2,2-diaryl-1-(oxa and thia)-2a-azonia-2-borataacenaphthene fungicidal

ABSTRACT

There are provided fungicidal 2,2-diaryl-1-(oxa and thia)-2a-azonia-2-borataacenaphthene compounds having the structural formula ##STR1## Further provided are compositions and methods comprising those compounds for the protection of plants from fungal infestation and disease.

BACKGROUND OF THE INVENTION

Phytopathogenic fungi are the causal agents for many diseases that infect and destroy crops. In particular, the diseases sugar beet cercospora leaf spot, apple scab, tomato early blight and grape and pepper botrytis are especially devastating.

Sugar beet is susceptible to many foliar diseases caused by phytopathogenic fungi. One of the most frequently encountered and destructive foliar diseases occurring on sugar beet is sugar beet cercospora leaf spot, caused by the fungus, Cercospora beticola. Sugar beet cercospora leaf spot is common to sugar beet plants throughout the world, and is particularly destructive in regions with wet, warm growing seasons, such as Western and Southern Europe, and the Midwestern United States. During periods of high temperature and wetness, sugar beet cercospora leaf spot spreads rapidly in the field. Ultimately, the disease kills sugar beet leaf tissue, resulting in reduced sugar beet weight and sugar content.

The leaves and fruit of apple trees are susceptible to attack by a fungus, Venturia inaequalis, resulting in a disease called apple scab. The disease is most common in the United States and Europe. Uncontrolled, apple scab results in deformed, low quality fruit.

In spite of the commercial fungicides available today, diseases caused by fungi still abound. Accordingly, there is ongoing research to create new and more effective fungicides for controlling or preventing diseases caused by phytopathogenic fungi.

It is therefore an object of the present invention to provide a method for the prevention, control or amelioration of a disease caused by a phytopathogenic fungus.

It is also an object of the present invention to provide a method for the protection of a plant, plant seed or tuber from fungal infestation and disease.

These and other objects of the present invention will become more apparent from the detailed description thereof set forth below.

SUMMARY OF THE INVENTION

The present invention describes fungicidal 2,2-diaryl-1-(oxa and thia)-2a-azonia-2-borataacenaphthene compounds.

The fungicidal 2,2-diaryl-1-(oxa and thia)-2a-azonia-2-borataacenaphthene compounds of the present invention have the following structural formula: ##STR2## wherein X and Y are each independently hydrogen, halogen, C₁ -C₆ alkoxy, C₁ -C₆ haloalkoxy, C₁ -C₆ alkyl or C₁ -C₆ haloalkyl;

m and n are each independently an integer of 0, 1, 2 or 3;

A is O or S;

R, R₁, R₂, R₃, R₄ and R₅ are each independently hydrogen, halogen, C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxy, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ hydroxyalkyl, cyano, nitro, CH₂ CN, hydroxy, NR₆ R₇, SO₃ R₈ or COR₉ ;

R₆, R₇ and R₈ are each independently hydrogen or C₁ -C₄ alkyl; and

R₉ is C₁ -C₄ alkyl.

This invention also relates to compositions and methods comprising those compounds for the prevention, control or amelioration of diseases caused by phytopathogenic fungi.

DETAILED DESCRIPTION OF THE INVENTION

Phytopathogenic fungi are the causal agents for many diseases that infect and destroy agronomic crops, both growing and harvested. In the United States alone, agronomic crops must compete with about 18,000 species of fungi.

Advantageously, the present invention provides a method for the prevention, control or amelioration of a disease caused by a phytopathogenic fungus by contacting said fungus with a fungicidally effective amount of a formula I, 2,2-diaryl-1-(oxa or thia)-2a-azonia-2-borataacenaphthene compound.

The present invention also provides a method for the protection of a plant, plant seed or tuber from fungal infestation and disease by applying to the plant, plant seed or tuber, or to the medium or water in which it is growing, a fungicidally effective amount of a formula I, 2,2-diaryl-1-(oxa or thia)-2a-azonia-2-borataacenaphthene compound.

The fungicidal 2,2-diaryl-1-(oxa and thia)-2a-azonia-2-borataacenaphthene compounds of the present invention have the following structural formula I: ##STR3## wherein X and Y are each independently hydrogen, halogen, C₁ -C₆ alkoxy, C₁ -C₆ haloalkoxy, C₁ -C₆ alkyl or C₁ -C₆ haloalkyl;

m and n are each independently an integer of 0, 1, 2 or 3;

A is O or S;

R, R₁, R₂, R₃, R₄ and R₅ are each independently hydrogen, halogen, C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxy, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ hydroxyalkyl, cyano, nitro, CH₂ CN, hydroxy, NR_(b) 6 R₇, SO₃ R₈ or COR₉ ;

R₆, R₇ and R₈ are each independently hydrogen or C₁ -C₄ alkyl; and

R₉ is C₁ -C₄ alkyl.

Preferred formula I fungicidal agents of the present invention are those wherein

X and Y are each independently hydrogen, halogen or C₁ -C₆ alkyl;

m and n are each independently an integer of 0, 1 or 2;

A is O;

R, R₁, R₂, R₃, R₄ and R₅ are each independently hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl, nitro, CH₂ CN, NR₆ R₇ or SO₃ R₈ ; and

R₆, R₇ and R₈ are each independently hydrogen or C₁ -C₄ alkyl.

Formula I 2,2-diaryl-1-oxa-2a-azonia-2-borataacenaphthene compounds which are particularly effective as fungicidal agents include

2,2-diphenyl-1-oxa-2a-azonia-2-borataacenaphthene;

2,2-di-p-tolyl-1-oxa-2a-azonia-2-borataacenaphthene;

2,2-bis(p-fluorophenyl)-1-oxa-2a-azonia-2-borataacenaphthene;

2,2-bis(p-tert-butylphenyl)-1-oxa-2a-azonia-2-borataacenaphthene;

3-methyl-2,2-diphenyl-1-oxa-2a-azonia-2-borataacenaphthene;

6-nitro-2,2-diphenyl-1-oxa-2a-azonia-2-borataacenaphthene;

7,9-dibromo-2,2-diphenyl-1-oxa-2a-azonia-2-borataacenaphthene;

6-chloro-2,2-di-p-tolyl-1-oxa-2a-azonia-2-borataacenaphthene; and

6,8-dichloro-2,2-di-p-tolyl-1-oxa-2a-azonia-2-borataacenaphthene, among others.

The term halogen used herein includes fluorine, chlorine, bromine and iodine. And the term "medium" used herein is defined as any environment, including but not limited to artificial nutrients or soil, in which a plant can be kept, live or thrive.

The fungicidal 2,2-diaryl-1-(oxa and thia)-2a-azonia-2-borataacenaphthene compounds of the present invention are particularly useful in the prevention, control or amelioration of diseases such as sugar beet cercospora leaf spot, apple scab, tomato early blight and grape or pepper botrytis. Such diseases are caused by the phytopathogenic fungi Cercospora beticola, Venturia inaequalis, Alternaria solani and Botrytis cinerea, respectively.

Fungicidal 2,2-diaryl-1-(oxa and thia)-2a-azonia-2-borataacenaphthene compounds of formula I may be prepared by reacting a substituted quinoline of formula II with a diarylborinic acid of formula III as shown in Flow Diagram I. ##STR4##

The formula I compounds are useful for controlling or preventing the growth of phytopathogenic fungi such as Cercospora beticola, Venturia inaequalis, Alternaria solani and Botrytis cinerea. Therefore, harmful diseases such as sugar beet cercospora leaf spot, apple scab, tomato early blight and grape and pepper botrytis may be prevented or controlled.

The formula I compounds are also useful for the protection of growing or harvested plants from the damage caused by phytopathogenic fungal disease when applied to said plants at a fungicidally effective rate. The effective rate will vary depending upon factors such as the virulence of the target fungus, the environment of the treatment and other ambient conditions. In practice, generally about 20 ppm to about 1,000 ppm, preferably about 50 ppm to about 500 ppm of the formula I compound may be dispersed in a liquid or solid carrier and applied to the plant, seed or tuber, or to the medium or water in which the plant, seed or tuber is growing.

The fungicidal compounds of the invention may be formulated as concentrated solutions, emulsifiable concentrates, flowable concentrates, microemulsions and the like. Said compounds may also be formulated as dry compacted granules, granular compositions, dusts, dust concentrates, suspension concentrates, wettable powders, and the like. Those formulations which lend themselves to seed, tuber, medium, water and/or foliage applications to provide the requisite plant protection are suitable. Such formulations include the compounds of the invention admixed with an inert solid or liquid carrier.

It is contemplated that the fungicidal compounds of the invention may be used in conjunction with, or in combination with, a pesticidally effective amount of one or more other pesticides, including but not limited to, anilazine, benalaxyl, benomyl, bitertanol, bordeaux mixture, carbendazim, carboxin, captafol, captan, chlorothalonil, cyproconazole, dichloran, diethofencarb, diniconazole, dithianon, dodine, edifenphos, fenarimol, fenbuconazole, fenfuram, fenpropidin, fenpropimorph, fentin hydroxide, ferbam, flusilazole, flusulfamide, flutriafol, folpet, fosetyl, fuberidazole, guazatine, hexaconazole, imazalil, iprobenfos, iprodione, mancozeb, maneb, metalaxyl, metiram, myclobutanil, nuarimol, ofurace, oxadixyl, oxycarboxin, penconazole, probenazole, prochloraz, propiconazole, pyrazophos, tebuconazole, thiabendazole, thiophanate, thiophanate-methyl, triadimefon, triadimenol, triarimol, tricyclazole, tridemorph, triflumizole, triforine, vinclozolin, zineb, and the like.

Where compositions of the invention are to be employed in combination treatments with other pesticidal agents, the composition may be applied concurrently as an admixture of the components as described above, or may be applied sequentially.

In order to facilitate a further understanding of the invention, the following examples are presented primarily for the purpose of illustrating more specific details thereof. The invention should not be deemed limited thereby except as defined in the claims.

EXAMPLE 1 Preparation of 2,2-Di-p-tolyl-1-oxa-2a-azonia-2-borataacenaphthene ##STR5##

A solution of [(bis-p-methyl)diphenyl]borinic acid (1.0 g, 4.7 mmol) in diethyl ether is added to a solution of 8-hydroxyquinoline (0.69 g, 4.7 mmol) in diethyl ether. The reaction mixture is stirred at room temperature for 30 minutes and filtered to obtain the title product as a yellow powder (1.1 g, mp 194°-195° C.).

Using essentially the same procedure, and employing the appropriately substituted diphenylborinic acid and 8-hydroxyquinoline, the following compounds are obtained:

    __________________________________________________________________________      ##STR6##                                                                      X     Y    R  R.sub.1                                                                              R.sub.3                                                                             R.sub.5                                                                               mp°C.                                   __________________________________________________________________________     CH.sub.3                                                                             CH.sub.3                                                                            H  H     Cl   Cl     220-223                                        CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.3                                                                          H     H    H      213-216                                        CH.sub.3                                                                             CH.sub.3                                                                            H  H     Cl   H       99-102                                        CH.sub.3                                                                             CH.sub.3                                                                            H  H     Br   Br     188-190                                        CH.sub.3                                                                             CH.sub.3                                                                            H  H     NO.sub.2                                                                            H      153-155                                        C(CH.sub.3).sub.3                                                                    C(CH.sub.3).sub.3                                                                   H  H     Cl   Cl     230-232                                        C(CH.sub.3).sub.3                                                                    C(CH.sub.3).sub.3                                                                   H  H     Cl   H      268-270                                        C(CH.sub.3).sub.3                                                                    C(CH.sub.3).sub.3                                                                   H  H     NO.sub.2                                                                            H      235-237                                        C(CH.sub.3).sub.3                                                                    C(CH.sub.3).sub.3                                                                   H  H     H    H      232- 234                                       C(CH.sub.3).sub.3                                                                    C(CH.sub.3).sub.3                                                                   CH.sub.3                                                                          H     H    H      201-203                                        F     F    H  H     Cl   H       95-97                                         F     F    H  H     CH.sub.2 CN                                                                         H      120-121                                        F     F    H  H     Cl   Br     178-180                                        F     F    H  H     NO.sub.2                                                                            H      137-139                                        F     F    H  H     Cl   Cl     152-154                                        F     F    CH.sub.3                                                                          H     H    H      139-142                                        F     F    H  H     H    H       99-101                                        H     H    H  H     SO.sub.3 H                                                                          I      249-250                                        H     H    H  H     NH.sub.2                                                                            H        215-215.5                                    H     H    H  H     H    (CH.sub.2).sub.2 CH.sub.3                                                               158-158.5                                    H     H    H  H     I    I      287-288                                        H     H    H  H     Cl   H      194.1-195                                      H     H    H  H     Cl   Cl     268.5-270                                      H     H    H  CH.sub.2 CH.sub.3                                                                    H    H      168-170                                        H     H    H  H     Cl   Br     269-271                                        H     H    H  H     H    Br     204-205                                        H     H    H  H     NO.sub.2                                                                            H      180-182                                        H     H    H  H     Br   Br     >270                                           H     H    H  H     H    H      201-202                                        H     H    CH.sub.3                                                                          H     H    H       176                                           __________________________________________________________________________

EXAMPLE 2 Evaluation of In Vivo Fungicidal Activity of Test Compounds

Test compounds are dissolved or suspended in acetone and diluted with deionized water containing about 0.05% TWEEN 20, a polyoxyethylene sorbitan monolaurate surfactant manufactured by Atlas Chemical Industries, to give a concentration of 200 ppm.

Host plants are sprayed with the test solution, dried and inoculated with fungi. When disease symptom development is optimal, the plants are rated for disease control according to the rating scale shown below. Each test contains inoculated treated plants, inoculated untreated plants and a reference standard. When more than one test is run, the data are averaged. The data obtained are shown in Table I.

Compounds employed in this in vivo fungicidal evaluation and in the in vitro fungicidal evaluation in the following example are given a compound number and identified by name. Data in Table I are reported by compound number.

    ______________________________________                                         RATING SCALE                                                                   Rating      Range % Control                                                    ______________________________________                                         0           0                                                                  1            1-14                                                              2           15-29                                                              3           30-44                                                              4           45-59                                                              5           60-74                                                              6           75-89                                                              7           90-95                                                              8           96-99                                                              9           100                                                                --          no evaluation                                                      ______________________________________                                         PHYTOPATHOGENIC FUNGI                                                          Symbol  Disease           Pathogen                                             ______________________________________                                         AS      Apple Scab        Venturia inaequalis                                  GDM     Grape Downy Mildew                                                                               Plasmopara viticola                                  PB      Pepper Botrytis   Botrytis cinerea                                     RB      Rice Blast        Pyricularia oryzae                                   SBC     Sugar Beet Cercospora                                                                            Cercospora beticola                                  TEB     Tomato Early Blight                                                                              Alternaria solani                                    WLR     Wheat Leaf Rust   Puccinia recondita                                                             f. sp. tritici                                       WPM     Wheat Powdery Mildew                                                                             Erysiphe graminis                                                              f. sp. tritici                                       WSN     Wheat Septoria Nodorum                                                                           Septoria nodorum                                             Blotch                                                                 ______________________________________                                         COMPOUNDS EVALUATED AS FUNGICIDAL AGENTS                                       Compound                                                                       No.                                                                            ______________________________________                                          1         3-Methyl-2,2-diphenyl-1-oxa-2a-azonia-2-                                       borataacenaphthene                                                   2         2,2-Diphenyl-1-oxa-2a-azonia-2-borata-                                         acenaphthene                                                         3         6-Nitro-2,2-diphenyl-1-oxa-2a-azonia-2-                                        borataacenaphthene                                                   4         7,9-Dibromo-2,2-diphenyl-1-oxa-2a-azonia-                                      2-borataacenaphthene                                                 5         2,2-Di-p-tolyl-1-oxa-2a-azonia-2-bora-                                         taacenaphthene                                                       6         3-Methyl-2,2-di-p-tolyl-1-oxa-2a-azonia-                                       2-borataacenaphthene                                                 7         6-Chloro-2,2-di-p-tolyl-1-oxa-2a-azonia-                                       2-borataacenaphthene                                                 8         6,8-Dichloro-2,2-di-p-tolyl-1-oxa-2a-                                          azonia-2-borataacenaphthene                                          9         6-Nitro-2,2-di-p-tolyl-1-oxa-2a-azonia-                                        2-borataacenaphthene                                                10         6,8-Dibromo-2,2-di-p-tolyl-1-oxa-2a-                                           azonia-2-borataacenaphthen                                          11         2,2-Bis-(p-fluorophenyl)-1-oxa-2a-azonia-                                      2-borataacenaphthene                                                12         2,2-Bis(p-fluorophenyl)-3-methyl-1-oxa-                                        2a-azonia-2-borataacenaphthene                                      13         6-Chloro-2,2-bis(p-fluorophenyl)-1-oxa-                                        2a-azonia-2-borataacenaphthene                                      14         6,8-Dichloro-2,2-bis(p-fluorophenyl)-1-                                        oxa-2a-azonia-2-borataacenaphthene                                  15         2,2-Bis(p-fluorophenyl)-6-nitro-1-oxa-                                         2a-azonia-2-borataacenaphthene                                      16         6-Chloro-2,2-diphenyl-1-oxa-2a-azonia-                                         2-borataacenaphthene                                                17         6,8-Dichloro-2,2-diphenyl-1-oxa-2a-                                            azonia-2-borataacenaphthene                                         18         2,2-bis(p-tert-butylphenyl)-1-oxa-2a-                                          azonia-2-borataacenaphthene                                         19         2,2-Bis(p-tert-butylphenyl)-3-methyl-                                          1-oxa-2a-azonia-2-borataacenaphthene                                20         2,2-Bis(p-tert-butylphenyl)-6-chloro-                                          1-oxa-2a-azonia-2-borataacenaphthene                                21         2,2-Bis(p-tert-butylphenyl)-6-nitro-1-                                         oxa-2a-azonia-2-borataacenaphthene                                  22         2,2-Bis(p-tert-butylphenyl)-6,8-dichloro-                                      1-oxa-2a-azonia-2-borataacenaphthene                                23         4-Ethyl-2,2-diphenyl-1-oxa-2a-azonia-2-                                        borataacenaphthene                                                  24         8-Bromo-6-chloro-2,2-diphenyl-1-oxa-2a-                                        azonia-2-borataacenaphthene                                         25         8-Bromo-2,2-diphenyl-1-oxa-2a-azonia-2-                                        borataacenaphthene                                                  26         8-Bromo-6-chloro-2,2-bis(p-fluorophenyl)-                                      1-oxa-2a-azonia-2-borataacenaphthene                                27         6-Amino-2,2-diphenyl-1-oxa-2a-azonia-2-                                        borataacenaphthene                                                  28         6,8-Diiodo-2,2-diphenyl-1-oxa-2a-azonia-                                       2-borataacenaphthene                                                29         8-Iodo-2,2-diphenyl-1-oxa-2a-azonia-2-                                         borataacenaphthene-6-sulfonic acid                                  30         2,2-Bis(p-fluorophenyl)-1-oxa-2a-azonia-                                       2-borataacenaphthene-7-aceonitrile                                  31         8-Propyl-2,2-diphenyl-1-oxa-2a-azonia-2-                                       borataacenaphthene                                                  ______________________________________                                    

                                      TABLE I                                      __________________________________________________________________________     In Vivo Fungicidal Evaluations                                                 Compound                                                                             Rate                                                                     Number                                                                               (ppm)                                                                              AS GDM PB                                                                               RB SBC                                                                               TEB                                                                               WLR WPM WSN                                        __________________________________________________________________________      1    200 9  8   9 0  0  4  7   0   --                                          2    200 9  9   9 9  8  8  9   0   --                                          3    200 6  0   8 0  8  4  0   8   --                                          4    200 0  5   0 0  0  0  0   0   --                                          5    200 9  9   9 0  7  9  0   0   --                                          6    200 6  7   6 0  0  6  0   0   --                                          7    200 7  0   9 0  0  4  0   0   --                                          8    200 6  7   0 0  0  0  0   0   --                                          9    200 6  0   6 0  6  4  8   4   --                                         10    200 0  0   0 0  0  0  0   0   --                                         11    200 9  9   9 8  8  9  9   0   --                                         12    200 9  7   7 8  6  8  9   6   --                                         13    200 9  9   7 6  0  9  8   6   --                                         14    200 9  6   6 6  0  6  8   7   --                                         15    200 9  5   0 6  0  8  8   0   --                                         16    200 8  0   9 6  8  8  0   0   --                                         17    200 6  0   0 0  5  4  0   0   --                                         18    200 8  9   9 6  8  4  --  0   8                                          19    200 8  6   0 4  0  0  --  0   2                                          20    200 7  0   9 0  7  0  --  0   0                                          21    200 8  0   0 0  8  0  --  4   0                                          22    200 7  0   0 0  7  2  --  4   0                                          23    200 8  7   9 6  8  9  --  0   0                                          24    200 0  0   0 0  7  0  --  0   0                                          25    200 8  9   9 4  8  9  --  0   7                                          26    200 0  5   0 4  4  0  --  6   0                                          27    200 4  3   2 0  0  0  --  0   0                                          28    200 0  0   0 0  0  0  --  0   0                                          29    200 0  0   7 0  0  0  --  0   0                                          30    200 8  6   8 8  5  0  --  7   5                                          31    200 7  4   7 0  7  4  --  0   0                                          __________________________________________________________________________

EXAMPLE 3 Evaluation of In Vitro Fungicidal Activity of Test Compounds

Test compounds are dissolved or suspended in acetone and dispersed into cell well plates containing a suspension of ground fungal mycelia in a nutrient broth. Assay plates are incubated for 3-4 days at 21° C. Growth inhibition is measured visually and is rated using the following scale:

    ______________________________________                                                Rating                                                                               % Inhibition                                                      ______________________________________                                                0     0                                                                        1      1-29                                                                    3     30-59                                                                    5     60-89                                                                    7     90-99                                                                    9     100                                                               ______________________________________                                    

Untreated controls, solvent blanks and reference standards are included in each test.

Assay fungi include the plant pathogens, Pythium ultimum (Pythul); Rhizoctonia solani (Rhizso); Fusarium oxysporum f. sp. cucumerinum (Fusoxc); and Pseudocercosporella herpotrichoides (Psdche).

When more than one test is run, the data are averaged. The data obtained are shown in Table II. The compounds evaluated are reported by compound number given in Example 2.

                                      TABLE II                                     __________________________________________________________________________     In Vitro Fungicidal Evaluations                                                Compound                                                                              Rate                                                                    Number (ppm)                                                                               FUSOXC PSDCHE PYTHUL RHIZSO                                        __________________________________________________________________________      1     25   5      7      9      9                                              2     25   3      0      5      7                                              3     25   5      8      7      7                                              4     25   7      0      1      5                                              5     25   3      5      0      7                                              6     25   3      0      0      0                                              7     25   9      7      3      7                                              8     25   7      9      7      9                                              9     25   9      9      9      9                                             10     25   9      5      0      7                                             11     25   5      7      7      5                                             12     25   7      5      5      9                                             13     25   7      9      9      9                                             14     25   9      7      7      9                                             15     25   9      9      9      7                                             16     25   5      9      7      9                                             17     25   7      7      5      9                                             18     25   9      9      9      9                                             19     25   0      0      0      0                                             20     25   0      0      0      0                                             21     25   5      9      7      7                                             22     25   7      9      7      9                                             23     25   3      5      5      5                                             24     25   9      7      5      9                                             25     25   7      9      9      9                                             26     25   9      9      9      7                                             27     25   7      0      7      5                                             28     25   3      0      0      5                                             29     25   9      7      7      5                                             30     25   5      0      7      7                                             31     25   1      0      3      3                                             __________________________________________________________________________ 

I claim:
 1. A method for the prevention, control or amelioration of a disease caused by a phytopathogenic fungus which comprises contacting said fungus with a fungicidally effective amount of a compound having the structural formula ##STR7## wherein X and Y are each independently hydrogen, halogen, C₁ -C₆ alkoxy, C₁ -C₆ haloalkoxy, C₁ -C₆ alkyl or C₁ -C₆ haloalkyl;m and n are each independently an integer of 0, 1, 2 or 3; A is O or S; R, R₁, R₂, R₃, R₄ and R₅ are each independently hydrogen, halogen, C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxy, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ hydroxyalkyl, cyano, nitro, CH₂ CN, hydroxy, NR₆ R₇, SO₃ R₈ or COR₉ ; R₆, R₇ and R₈ are each independently hydrogen or C₁ -C.sub. 4alkyl; and R₉ is C₁ -C₄ alkyl.
 2. The method according to claim 1 wherein A is O.
 3. The method according to claim 2 whereinX and Y are each independently hydrogen, halogen or C₁ -C₆ alkyl; m and n are each independently an integer of 0, 1 or 2; R, R₁, R₂, R₃, R₄ and R₅ are each independently hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl, nitro, CH₂ CN, NR₆ R₇ or SO₃ R₈ ; and R₆, R₇ and R₈ are each independently hydrogen or C₁ -C₄ alkyl.
 4. The method according to claim 3 wherein the compound is selected from the group consisting of2,2-diphenyl-1-oxa-2a-azonia-2-borataacenaphthene; 2,2-di-p-tolyl-1-oxa-2-azonia-2-borataacenaphthene; 2,2-bis(p-fluorophenyl)-1-oxa-2a-azonia-2-borataacenaphthene; 2,2-bis(p-tert-butylphenyl)-1-oxa-2a-azonia-2-borataacenaphthene; 3-methyl-2,2-diphenyl-1-oxa-2a-azonia-2-borataacenaphthene; 6-nitro-2,2-diphenyl-1-oxa-2a-azonia-2-borataacenaphthene; 7,9-dibromo-2,2-diphenyl-1-oxa-2a-azonia-2-borataacenaphthene; 6-chloro-2,2-di-p-tolyl-1-oxa-2a-azonia-2-borataacenaphthene; and 6,8-dichloro-2,2-di-p-tolyl-1-oxa-2a-azonia-2-borataacenaphthene.
 5. The method according to claim 1 wherein the compound is applied at a concentration of about 20 ppm to 1,000 ppm.
 6. The method according to claim 1 wherein said disease is sugar beet cercospora leaf spot, apple scab, tomato early blight, or grape or pepper botrytis.
 7. A method for the protection of a plant, plant seed or tuber from fungal infestation and disease which comprises applying to the plant, plant seed or tuber, or to the medium or water in which it is growing, a fungicidally effective amount of a compound having the structural formula ##STR8## wherein X and Y are each independently hydrogen, halogen, C₁ -C₆ alkoxy, C₁ -C₆ haloalkoxy, C₁ -C₆ alkyl or C₁ -C₆ haloalkyl;m and n are each independently an integer of 0, 1, 2 or 3; A is O or S; R, R₁, R₂, R₃, R₄ and R₅ are each independently hydrogen, halogen, C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxy, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ hydroxyalkyl, cyano, nitro, CH₂ CN, hydroxy, N₆ R₇, SO₃ R₈ or COR₉ ; R₆, R₇ and R₈ are each independently hydrogen or C₁ -C₄ alkyl; and R₉ is C₁ -C₄ alkyl.
 8. The method according to claim 7 whereinA is O; and R, R₁, R₂, R₃, R₄ and R₅ are each independently hydrogen, halogen, C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxy, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ hydroxyalkyl, nitro, CH₂ CN, hydroxy, NR₆ R₇ or SO₃ R₈.
 9. The method according to claim 8 whereinX and Y are each independently hydrogen, halogen or C₁ -C₆ alkyl; m and n are each independently an integer of 0, 1 or 2; and R, R₁, R₂, R₃, R₄ and R₅ are each independently hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl, nitro, CH₂ CN, NR₆ R₇ or SO₃ R₈.
 10. The method according to claim 9 wherein the compound is selected from the group consisting of2,2-diphenyl-1-oxa-2a-azonia-2-borataacenaphthene; 2,2-di-p-tolyl-1-oxa-2-azonia-2-borataacenaphthene; 2,2-bis(p-fluorophenyl)-1-oxa-2a-azonia-2-borataacenaphthene; 2,2-bis(p-tert-butylphenyl)-1-oxa-2a-azonia-2-borataacenaphthene; 3-methyl-2,2-diphenyl-1-oxa-2a-azonia-2-borataacenaphthene; 6-nitro-2,2-diphenyl-1-oxa-2a-azonia-2-borataacenaphthene; 7,9-dibromo-2,2-diphenyl-1-oxa-2a-azonia-2-borataacenaphthene; 6-chloro-2,2-di-p-tolyl-1-oxa-2a-azonia-2-borataacenaphthene; and 6,8-dichloro-2,2-di-p-tolyl-1-oxa-2a-azonia-2-borataacenaphthene. 